JP4061573B2 - Conductive catalyst particle manufacturing method, gas diffusing catalyst electrode manufacturing method, and apparatus used for conductive catalyst particle manufacturing method - Google Patents

Description

[0001]
[Technical field to which the invention belongs]
  The present invention relates to a method for producing conductive catalyst particles, a method for producing gas diffusible catalyst electrodes, and an apparatus used for a method for producing conductive catalyst particles.
[0002]
[Prior art]
Conventionally, a gas diffusive catalyst electrode is formed by molding catalyst particles in which platinum as a catalyst is supported on carbon as a conductive powder together with, for example, a fluororesin and an ion conductor as a water repellent resin (special feature). No. 5-36418) or manufactured through a process of coating on a carbon sheet.
[0003]
When this electrode is used as an electrode for hydrogen decomposition constituting a fuel cell such as a polymer electrolyte fuel cell, the fuel is ionized by a catalyst such as platinum, and the generated electrons flow through conductive carbon, and hydrogen Proton (H⁺) Flows to the ion conducting membrane through the ion conductor. Here, a gap through which gas passes, carbon through which electricity passes, an ion conductor through which ions pass, and a catalyst material for ionizing fuel and oxidant are required.
[0004]
Usually, as a method of attaching platinum (catalyst substance) to the surface of carbon powder as conductive powder, first, platinum is ionized into a liquid state, and carbon powder is immersed in a solution containing platinum. There is a method in which platinum is attached to the body, followed by reduction and heat treatment, so as to adhere as fine particle platinum on the surface of the carbon powder (Japanese Patent No. 2879649).
[0005]
[Course to Invention]
However, the conventional method as described above requires reduction and heat treatment to support platinum on the carbon powder. For example, when the temperature in this heat treatment is low, the crystallinity of platinum deteriorates, There is a problem that good catalytic properties cannot be obtained.
[0006]
In addition, the fuel is ionized by the catalyst material such as platinum as described above, and the generated electrons flow through the conductive carbon, and protons (H generated by ionizing hydrogen)⁺) Flows to the ion conducting membrane through the ion conductor. Accordingly, since the carbon powder and the ionic conductor need to be in contact with each other, the ionic conductor is usually applied after platinum is supported on the carbon powder. However, since platinum (catalyst substance) functions only in the part in contact with the gas, platinum (catalyst substance) having no contact part with the gas by the ion conductor does not function.
[0007]
As an alternative, there is a method of supporting platinum after applying an ion conductor to carbon powder. However, heat treatment must be performed to improve the crystallinity of platinum. However, since ion conductors generally have low heat resistance, when heated to a heat treatment temperature that improves the crystallinity of platinum, the ion conductor Will deteriorate.
[0008]
FIG. 11 (A) is a schematic cross-sectional view showing conductive catalyst particles obtained by supporting platinum 18 on carbon powder 1 by a conventional manufacturing method, and FIG. 11 (B) shows carbon powder 1 FIG. 3 is a schematic cross-sectional view showing conductive catalyst particles obtained by attaching platinum conductor 18 on the ion conductor 19 after the ion conductor 19 is attached thereto.
[0009]
As is clear from FIG. 11 (A), the platinum-supported conductive catalyst particles carrying platinum obtained from the liquid phase are present in a spherical shape on the surface of the carbon powder 1. It is easy to move away from the surface of the metal and requires a large amount of platinum in the production process. Further, since the platinum 18 exists in a spherical shape, only the surface of the platinum 18 functions as a catalytic substance, the inside does not function, and the efficiency of the catalytic activity is low with respect to the amount of platinum. Although not shown, platinum 18 also enters the pores existing on the surface of the carbon powder 1.
[0010]
Further, as shown in FIG. 11B, when the platinum 18 is supported after the ion conductor 19 is applied to the carbon powder, the heat treatment for improving the crystallinity of the platinum 18 is necessary as described above. However, the ionic conductor 19 generally has low heat resistance, and when heated to a heat treatment temperature that improves the crystallinity of the platinum 18, the ionic conductor 19 is deteriorated.
[0011]
As a result of intensive studies to solve the above-described problems, the present inventors have proposed a gas diffusive catalytic electrode having a good catalytic action with a smaller amount of catalyst in Japanese Patent Application No. 2000-293517.
[0012]
That is, according to the invention according to Japanese Patent Application No. 2000-293517 (hereinafter referred to as the prior application invention), the surface of the conductive powder 1 is applied to the surface of the conductive powder 1 using a physical vapor deposition method such as a sputtering method as shown in FIG. By attaching the catalyst substance, conductive catalyst particles having the catalyst substance 18 attached only to the surface of the conductive powder 1 as shown in FIG. 13 can be obtained.
[0013]
That is, as shown in FIG. 13A, when the physical vapor deposition method is used, the catalyst material 18 is attached only to the surface of the conductive powder 1 in the conductive catalyst particles obtained by this. Therefore, good catalytic action can be obtained with a smaller amount, and a sufficient contact area between the catalytic substance 18 and the gas is ensured, so that the specific surface area of the catalytic substance 18 contributing to the reaction is increased, and the catalytic ability is increased. Will also improve.
[0014]
Further, as shown in FIG. 13B, an ion conductor 19 is attached to the surface of the conductive powder 1, and a catalyst substance 18 is attached to the surface of the ion conductor 19 by physical vapor deposition. However, since the catalyst material 18 is deposited by physical vapor deposition, it is not necessary to perform a heat treatment for improving the crystallinity of the catalyst material as in the prior art, and the performance of the ion conductor 19 is not impaired. Can be attached.
[0015]
[Problems to be solved by the invention]
However, the present inventor has found that the invention of the prior application has points to be improved while having the above-described excellent features.
[0016]
As shown in FIG. 12, according to the manufacturing method according to the prior invention, the catalyst substance is attached only to the surface of the conductive powder 1 by physical vapor deposition such as sputtering. At this time, the catalyst substance only adheres to the conductive powder 1 existing on the outermost surface of the container 4, and it is difficult to uniformly apply the catalyst substance to the entire conductive powder arranged in the container 4. It was.
[0017]
  The present invention has been made in order to improve the insufficiency while taking advantage of the above-mentioned features of the invention of the prior application, and its purpose is to uniformly attach a catalytic substance to all conductive powders. An object of the present invention is to provide a device for use in a method for producing conductive catalyst particles, a method for producing gas diffusible catalyst electrodes, and a method for producing conductive catalyst particles.
[0018]
[Means for Solving the Problems]
  That is, according to the present invention, when the catalyst material is adhered to the surface of the conductive powder by physical vapor deposition while vibrating the conductive powder, the conductive powder and the vibration amplification means are placed on the vibration surface. Method for producing conductive catalyst particles, which are arranged in the same and vibrate them simultaneouslyIn,According to a method for producing conductive catalyst particles, an ion conductor is attached to a surface of the conductive powder, and further, the catalyst substance is attached to the surface of the ion conductor by the physical vapor deposition method. Is.
  AlsoIn order to carry out the method for producing conductive catalyst particles of the present invention, vibration means for vibrating the conductive powder, physical vapor deposition means for attaching a catalyst substance to the surface of the conductive powder, and amplification of the vibration An apparatus for producing conductive catalyst particles,In the conductive catalyst particles, the ionic conductor is attached to the surface of the conductive powder, and the catalyst substance is further attached to the surface of the ionic conductor by the physical vapor deposition method. In production equipmentIt is concerned.
[0022]
  Further, the conductive powder and the vibration amplifying means are disposed on the vibration surface, and while vibrating them, the catalyst material is adhered to the surface of the conductive powder by physical vapor deposition to form the conductive catalyst particles. And a method for producing a gas diffusible catalyst electrode comprising the steps of: obtaining a gas diffusible catalyst electrode containing the obtained conductive catalyst particles.In the gas diffusive catalytic electrode, an ion conductor is attached to the surface of the conductive powder, and the catalyst substance is further attached to the surface of the ion conductor by the physical vapor deposition method. In manufacturing methodIt is concerned.
[0023]
According to the present invention, the catalyst material is disposed on the surface of the conductive powder by the physical vapor deposition while the conductive powder and the vibration amplifying unit are disposed on the vibration surface and are vibrated. Therefore, the conductive powder is more vibrated and sufficiently mixed, and does not stay at one place on the vibration surface. Accordingly, not only the surface of the powder layer but also the inside of the conductive powder comes to the surface, and the catalyst substance can be uniformly attached to all the conductive powders.
[0024]
  In addition, since the catalyst material is attached to the surface of the conductive powder by the physical vapor deposition method, the catalyst material having good crystallinity is deposited only on the surface of the conductive powder at a low temperature (that is, the conductive material). The conductive catalyst particles obtained can adhere to the catalyst powder in a smaller amount, and can adhere to the catalyst material and the gas. Is sufficiently secured, the specific surface area of the catalytic substance contributing to the reaction is increased, and the catalytic performance is also improved.
  In addition, the ionic conductor is adhered to the surface of the conductive powder, and the catalytic material is further adhered to the surface of the ionic conductor by the physical vapor deposition method, so that the crystallinity of the catalytic material is good. It is not necessary to perform heat treatment to make the catalyst material, and the catalyst substance can be adhered without impairing the performance of the ion conductor.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described more specifically based on embodiments.
[0026]
As the physical vapor deposition method, it is desirable to use a sputtering method using the catalyst material as a target. The sputtering method can be easily produced, has high productivity, and has good film formability.
[0027]
In addition to the sputtering method, a pulse laser deposition method may be used as the physical vapor deposition method. The pulse laser deposition method is easy to control in film formation and has good film formability.
[0028]
Since the catalyst material is deposited by the sputtering method or the pulse laser deposition method, the catalyst material having good crystallinity is present only on the surface of the conductive powder (that is, in the conductive powder at a low temperature). The conductive catalyst particles obtained can be obtained in a smaller amount and have good catalytic action, and the contact area between the catalyst substance and the gas is sufficient. Thus, the specific surface area of the catalytic substance contributing to the reaction is increased, and the catalytic ability can be improved.
[0029]
The physical means may be at least one of a vacuum deposition apparatus, a sputtering apparatus, and a pulse laser deposition apparatus.
[0030]
  Here, in Japanese Patent Laid-Open No. 11-510311, an example is described in which a noble metal is sputter-deposited on a carbon sheet. However, in the production method according to the present invention, the catalyst substance is applied to the surface of a conductive powder. Since it is adhered, the specific surface area of the catalyst substance contributing to the reaction can be increased and the catalytic performance can be improved as compared with the above-mentioned Japanese National Patent Publication No. 11-510311.In the following description, an ion conductor is attached to the surface of the conductive powder, but for convenience, the description and illustration of the ion conductor may be omitted.
[0031]
FIG. 1 is a schematic sectional view of an apparatus for producing conductive catalyst particles according to the present invention.
[0032]
As shown in FIG. 1, when the catalyst material is adhered to the surface of the conductive powder 1 by the sputtering method using the catalyst material as a target 2 as the physical vapor deposition method, for example, the vibration amplification means The ball 3 having a smooth surface is used, and the conductive powder 1 and the ball 3 are mixed and placed on the vibration surface 20 in the same container 4 having a substantially flat bottom surface. The vibration is preferably applied by a vibrator 5 made of a horn. By using the vibration device 21 configured as described above, the conductive powder 1 collides with the ball 3, mixes and flows, and does not stay at one place on the vibration surface. Then, by the sputtering method, not only the surface of the powder layer of the conductive powder 1 but also the inside of the container 4 is exposed to the surface in the container 4, and is more uniform with respect to the entire conductive powder 1. The catalyst material can be adhered to the substrate.
[0033]
In this case, the ball 3 is preferably a ceramic or metal ball having a diameter of 1 to 10 mm.
[0034]
FIG. 2 shows a schematic view of the container 4 in which the conductive powder and the ball as the vibration amplifying means are arranged, and the total area A of the balls with respect to the area S of the distribution area of the conductive powder. The ratio is preferably 30 to 80%. If this ratio is too small, mixing of the conductive powder 1 will be insufficient, and if it is too large, the ratio of the conductive powder 1 will be small and the adhesion efficiency of the catalytic material by sputtering will be deteriorated, and the catalytic material will adhere. The production efficiency of the catalyst particles is insufficient.
[0035]
FIG. 3 shows a partially enlarged schematic cross-sectional view of a container 4 in which the conductive powder 1 and the ball 3 as the vibration amplifying means are arranged, and the vibration with respect to the layer thickness t formed by the conductive powder 1. It is preferable that the diameter R of the ball 3 as the amplifying means is 10 to 70%. If the diameter is out of the range, it is disadvantageous for the same reason as in the case of the area ratio.
[0036]
Moreover, the frequency of the vibration applied to the conductive powder 1 and the ball 3 as the vibration amplification means by the vibrator 5 is 5 to 200 Hz in order to mix the conductive powder 1 sufficiently. The amplitude of the vibration is preferably ± (0.5 to 20) mm for the same reason (hereinafter, the same applies to other embodiments).
[0037]
If the catalyst material is adhered to the surface of the conductive powder, for example, by the sputtering method in an environment within each preferable range of conditions as described above, the conductive powder is further improved. Therefore, the catalyst substance can be more uniformly attached to the surface of the conductive powder. When deviating from the above ranges, that is, when the ball diameter is less than 1 mm or more than 10 mm, when the frequency is less than 5 Hz or more than 200 Hz, or when the amplitude is less than ± 0.5 mm In such a case, the conductive powder cannot vibrate well, and the conductive powder stays at the bottom of the container without flowing, resulting in a non-uniform film formation. Sometimes. In addition, when the amplitude exceeds 20 mm, the conductive powder may jump out and the yield may be reduced.
[0038]
In the manufacturing method according to the present invention, instead of the ball, as the vibration amplification means, a wire is integrally formed so as to form a substantially spiral, substantially concentric or substantially folded pattern when viewed in plan. And at least a part of this part is placed on the bottom surface of the container in a non-fixed state (this non-fixed state is a state in which it itself freely vibrates in three dimensions: the same applies hereinafter) The conductive powder may be disposed on the component and subjected to the vibration.
[0039]
FIG. 4 is a schematic view of a vibration device according to the present invention using, as the vibration amplifying means, a component 6 integrally formed so that a wire forms a spiral pattern when seen in a plan view.
[0040]
FIG. 5 shows a vibration according to the present invention, in which the component 7 is integrally formed (that is, radially connected) so that the wire forms a concentric pattern in plan view as the vibration amplifying means. It is a schematic sectional drawing of an apparatus.
[0041]
FIG. 6 is a schematic cross-sectional view of a vibration device according to the present invention using, as the vibration amplification means, a component 8 that is integrally formed so that a wire forms a folded pattern when seen in a plan view.
[0042]
In any case shown in FIGS. 4 to 6, the component 6, 7 or 8 is placed on the bottom surface of the container 4 in an unfixed state, and the conductive powder 1 is placed on the component 6, 7 or 8. When placed and subjected to the vibration, the shape of the component 6, 7 or 8 vibrates while being held, so that the conductive powder 1 can be further vibrated and flow better. At this time, if the catalyst material is attached to the surface of the conductive powder 1 by the physical vapor deposition method such as the sputtering method, the conductive powder 1 in the container 4 is not only the surface but also the internal one. In addition, the catalyst substance can be uniformly deposited over the entire surface.
[0043]
  In obtaining such an effect, the wire formed in a spiral, concentric or folded pattern is a metal wire having a diameter of 1 to 10 mm, and the spiral, concentric or folded pattern is formed in the pattern. The outer diameter of the component is preferably 5 mm smaller than the inner diameter of the container, and the pattern pitch is preferably 5 to 15 mm. When the conditions deviate from these values, the mixing of the conductive powder 1 tends to be insufficient, and the adhesion efficiency of the catalyst substance tends to decrease.
[0044]
Further, for the same reason as the case of using the above-described ball, the wire as the vibration amplifying means has a spiral shape, a concentric shape, or a folded shape as viewed in a plane with respect to the layer thickness formed by the conductive powder. It is preferable that the thickness of the parts integrally formed so as to form a pattern is 10 to 70%.
[0045]
  AboveAs shown in FIG. 13 (A), the conductive catalyst particles that can be obtained by the manufacturing method are such that the catalyst substance 18 does not enter pores (not shown) present on the surface of the conductive powder 1, for example. It adheres only to the surface of the conductive powder 1. Accordingly, a good catalytic action can be obtained with a smaller amount of catalyst, and a sufficient contact area between the catalyst substance 18 and the gas is ensured, so that the specific surface area of the catalyst substance 18 contributing to the reaction is increased, and the catalyst The performance is also improved.
[0046]
  FIG. 13 (B)Shows conductive catalyst particles obtained by the production method of the present invention.The ion conductor 19 is attached to the surface of the conductive powder 1, and the catalyst substance 18 is attached to the surface of the ion conductor 19 by the physical vapor deposition method.HaveThe In this case, since the catalyst material 18 is attached by the physical vapor deposition method, it is not necessary to perform a heat treatment for improving the crystallinity of the catalyst material 18 as in the prior art, and without impairing the performance of the ion conductor 19, A catalytic material 18 can be deposited.
[0047]
  Each of the conductive catalyst particles of (A) and (B) shown in FIG. 13 exhibits 10 to 1000 weight of the catalyst substance 18 with respect to the conductive powder 1 in order to exhibit both catalytic ability and conductivity. %, And the catalyst material 18 includes Pt, IrOrRhConsist ofIt is preferable to use a noble metal material.
[0048]
The electric resistance of the conductive powder 1 is 10^-3Ω · m or less is preferable, carbon, ITO (indium tin oxide: indium oxide doped with tin) and SnO₂It is preferable to use at least one of them.
[0049]
When carbon is used as the conductive powder 1, the specific surface area of this carbon is 300 m.²/ G or more, preferably 300 m²When it is less than / g, the characteristics as the conductive catalyst particles may be deteriorated.
[0050]
Further, when the gas diffusive catalyst electrode is produced using the conductive catalyst particles, gas permeability is an important performance. When carbon is used as the conductive powder 1, the oil absorption amount of the carbon is reduced. Good gas permeability can be obtained by setting it as 200 ml / 100g or more.
[0051]
The conductive catalyst particles obtained by the production method according to the present invention can themselves form a catalyst layer by press working or the like. However, when the conductive catalyst particles are formed by binding with a resin, the conductive catalyst powder is made porous. Since it can hold | maintain with sufficient intensity | strength on a gas-permeable electrical power collector, it is more preferable on manufacture of the said gas-diffusible catalyst electrode.
[0052]
As described above, the gas diffusive catalyst electrode is substantially composed of only the conductive catalyst particles, or other components such as a resin for binding the particles in addition to the conductive catalyst particles. May be contained. In the latter case, the other component includes a water-repellent resin (for example, fluorine-based) in terms of binding and drainage, and a pore-forming agent (for example, CaCO in terms of gas permeability)._Three) And an ion conductor or the like in terms of mobility such as protons. Furthermore, it is preferable to hold the conductive catalyst particles on a porous gas-permeable current collector (for example, a carbon sheet).
[0053]
The gas diffusive catalyst electrode obtained by the production method according to the present invention can be applied to an electrochemical device configured as a fuel cell or a hydrogen production apparatus.
[0054]
That is, in a basic structure composed of a first pole, a second pole, and an ionic conductor sandwiched between the two poles, at least the first pole of the first pole and the second pole is the present invention. The gas diffusive catalyst electrode obtained by the production method based on the above can be applied.
[0055]
More specifically, the gas diffusible catalyst electrode obtained by the production method according to the present invention is preferably applied to an electrochemical device or the like in which at least one of the first electrode and the second electrode is a gas electrode. Is possible.
[0056]
FIG. 7 shows a fuel cell of a specific example using the gas diffusive catalyst electrode. Here, the catalyst layer 9 in FIG. 7 is the conductive layer in which the catalytic substance (for example, platinum) is attached only to the surface of the conductive powder (for example, carbon powder) obtained by the manufacturing method according to the present invention. In addition to the conductive catalyst particles, in some cases, an ion conductor, a water-repellent resin (for example, fluorine-based), and a pore-forming agent (CaCO_ThreeThe gas diffusive catalyst electrode obtained by the production method according to the present invention comprises a catalyst layer 9 and, for example, a carbon sheet 10 as a porous gas permeable current collector. This is a porous gas diffusible catalyst electrode. However, in a narrow sense, only the catalyst layer 9 may be referred to as a gas diffusing catalyst electrode. Moreover, the ion conduction part 11 is pinched | interposed between the 1st pole using the said gas-diffusible catalyst electrode, and a 2nd pole.
[0057]
This fuel cell is provided with a negative electrode (fuel electrode or hydrogen electrode) 13 using the gas diffusible catalyst electrode obtained by the manufacturing method according to the present invention, which has a terminal 12 facing each other, and a terminal 14. The gas diffusible catalyst electrode obtained by the production method based on the above (however, it is not necessarily used for the positive electrode) has a positive electrode (oxygen electrode) 15, and the ion conducting portion 11 is between these two electrodes. It is pinched. In use, H on the negative electrode 13 side₂Hydrogen is passed through the channel 16. Fuel (H₂) Generate hydrogen ions while passing through the flow path 16, and these hydrogen ions move to the positive electrode 15 side together with the hydrogen ions generated at the negative electrode 13 and the hydrogen ions generated at the ion conducting portion 11, where O₂It reacts with oxygen (air) passing through the flow path 17 and thereby a desired electromotive force is taken out.
[0058]
Such a fuel cell has good catalytic action because the gas diffusive catalyst electrode obtained by the production method according to the present invention constitutes the first electrode and the second electrode, and the catalyst substance And gas (H₂) Is sufficiently secured, the specific surface area of the catalyst substance contributing to the reaction is increased, the catalytic ability is improved, and good output characteristics are obtained. In addition, hydrogen ions are dissociated in the negative electrode 13, and hydrogen ions are dissociated in the ion conducting unit 11, and hydrogen ions supplied from the negative electrode 13 side move to the positive electrode 15 side, so that the hydrogen ion conductivity is high. There are features.
[0059]
FIG. 8 shows a hydrogen production apparatus of a specific example in which the gas diffusible catalyst electrode obtained by the production method according to the present invention is used for the first electrode and the second electrode.
[0060]
Here, the reaction in each electrode is shown below.
Positive electrode: H₂O → 2H⁺+ 1 / 2O₂+ 2e^-
Negative electrode: 2H⁺+ 2e^-→ H₂↑
The required theoretical voltage is 1.23V or higher.
[0061]
The catalyst layer 9 ′ in FIG. 8 is the conductive catalyst in which the catalyst substance (for example, platinum) is attached only to the surface of the conductive powder (for example, carbon powder) obtained by the manufacturing method according to the present invention. In addition to particles, in some cases, ion conductors, water-repellent resins (for example, fluorine-based), and pore formers (CaCO_ThreeThe gas diffusive catalyst electrode obtained by the production method according to the present invention includes a catalyst layer 9 ′ and, for example, a carbon sheet 10 ′ as a porous gas-permeable current collector. Is a porous gas diffusive catalyst electrode. Further, an ion conducting portion 11 ′ is sandwiched between the first electrode using the gas permeable catalyst electrode and the second electrode.
[0062]
In use, this hydrogen production apparatus is supplied with water vapor or water vapor-containing air on the positive electrode 15 ′ side, and the water vapor or water vapor-containing air is decomposed on the positive electrode 15 ′ side to generate electrons and protons (hydrogen ions). The generated electrons and protons move to the negative electrode 13 ′ side, and are converted into hydrogen gas on the negative electrode 13 ′ side, whereby desired hydrogen gas is generated.
[0063]
In such a hydrogen production apparatus, the gas diffusive catalyst electrode obtained by the production method according to the present invention constitutes at least the first electrode of the first electrode and the second electrode. Protons and electrons necessary for generating hydrogen can smoothly move in the electrode.
[0064]
Used in the gas diffusive catalyst electrode obtained by the production method according to the present invention, or in the ion conducting portion sandwiched between both the first electrode and the second electrode constituting the electrochemical device. Examples of the possible ion conductor include fullerene derivatives such as fullerenol (polyhydroxide fullerene) in addition to general Nafion (perfluorosulfonic acid resin manufactured by DuPont).
[0065]
As shown in FIG. 9, fullerenol having a structure in which a plurality of hydroxyl groups are added to a fullerene molecule was first reported in 1992 by Chiang et al. (Chiang, LY; Swirczewski, JW; Hsu, CS). ; Chowdhury, SK; Cameron, S .; Creegan, K., J. Chem. Soc, Chem. Commun. 1992, 1791).
[0066]
The present applicant makes such fullerenol an aggregate as schematically shown in FIG. 10 (A), so that an interaction occurs between the hydroxyl groups of the adjacent fullerenol molecules (in the figure, ◯ indicates a fullerene molecule). As a result, this aggregate is a macro aggregate and has high proton conductivity (in other words, H from the phenolic hydroxyl group of the fullerenol molecule).⁺For the first time.
[0067]
In addition to the above fullerenol, for example, a plurality of OSO_ThreeAggregates of fullerene having an H group can also be used as the ionic conductor. OH group is OSO_ThreeA polyhydroxylated fullerene as shown in FIG. 10 (B), ie, a hydrogen sulfate esterified fullerenol, replaced with an H group was also reported in 1994 by Chiang et al. (Chiang.LY; Wang, LY; Swirczewski, JW Soled, S .; Cameron, S., J. Org. Chem. 1994, 59, 3960). Hydrogen sulfate esterified fullerene has an OSO in one molecule._ThreeSome include only the H group, or a plurality of each of these groups and hydroxyl groups can be provided.
[0068]
When many of the above-mentioned fullerenol and hydrogen sulfate esterified fullerenol are agglomerated, the proton conductivity that is shown as a bulk is the large amount of hydroxyl groups and OSO originally contained in the molecule._ThreeSince protons derived from the H group are directly involved in movement, it is not necessary to take in hydrogen or protons originating from water vapor molecules from the atmosphere, and it is also necessary to replenish moisture from the outside, especially to absorb moisture from the outside air. There are no restrictions on the atmosphere. Therefore, it can be used continuously even in a dry atmosphere.
[0069]
In addition, fullerene, which is the base of these molecules, has particularly electrophilic properties, which is a highly acidic OSO._ThreeIt is considered that not only the H group but also the hydroxyl group or the like greatly contributes to the promotion of ionization of hydrogen ions, and exhibits excellent proton conductivity. In addition, a large number of hydroxyl groups and OSO are contained in one fullerene molecule._ThreeSince an H group or the like can be introduced, the number density of protons involved in conduction per unit volume of the conductor is extremely increased, so that effective conductivity is exhibited.
[0070]
Most of the above-mentioned fullerenol and hydrogen sulfate esterified fullerenol are composed of carbon atoms of fullerene, and thus are light in weight, hardly change in quality, and contain no pollutants. Fullerene production costs are also rapidly decreasing. From the viewpoint of resources, environment, and economy, fullerene is considered to be a near ideal carbon-based material more than any other material.
[0071]
In addition, fullerene molecules may include,_ThreeIn addition to H, -COOH, -SO_ThreeH, -OPO (OH)₂Those having any of the above can also be used.
[0072]
In order to synthesize the fullerenol and the like, a desired group may be introduced into the constituent carbon atoms of the fullerene molecule by appropriately combining known treatments such as acid treatment and hydrolysis with the fullerene molecule powder. it can.
[0073]
Here, when the fullerene derivative is used as the ionic conductor constituting the ionic conduction part, the ionic conductor may be substantially made of only the fullerene derivative or bound by a binder. preferable.
[0074]
Instead of the ionic conductor sandwiched between the first electrode and the second electrode, which is composed only of the film-like fullerene derivative obtained by pressure-molding the fullerene derivative, the binder is bound by a binder. Any fullerene derivative may be used for the ion conducting portion 5. In this case, an ion conducting portion having sufficient strength can be formed by being bound by the binder.
[0075]
Here, as the polymer material that can be used as the binder, one or two or more kinds of polymers having a known film-forming property are used, and the compounding amount in the ion conductive part is usually 20% by weight. Keep it below. This is because if it exceeds 20% by weight, the conductivity of hydrogen ions may be reduced.
[0076]
Since the ion conducting part having such a configuration also contains the fullerene derivative as an ion conductor, it can exhibit the same hydrogen ion conductivity as the above-described ion conductor consisting essentially of the fullerene derivative.
[0077]
In addition, unlike the case of fullerene derivative alone, it has film-forming properties derived from polymer materials, and has a higher strength and more flexible ion conduction than gas fullerene derivative powder compression molded products. Can be used as a conductive thin film (thickness is usually 300 μm or less).
[0078]
The polymer material is not particularly limited as long as it does not inhibit hydrogen ion conductivity as much as possible (by reaction with the fullerene derivative) and has film-forming properties. Usually, those having no electronic conductivity and good stability are used. Specific examples thereof include polyfluoroethylene, polyvinylidene fluoride, polyvinyl alcohol and the like, and these are preferable polymer materials for the following reason.
[0079]
First, polyfluoroethylene is preferable because a thin film having a higher strength can be easily formed with a small amount of blending than other polymer materials. In this case, the blending amount is as small as 3% by weight or less, preferably 0.5 to 1.5% by weight, and the thickness of the thin film can be reduced from 100 μm to 1 μm.
[0080]
Moreover, the reason why polyvinylidene fluoride and polyvinyl alcohol are preferred is that an ion conductive thin film having a better gas permeation preventing ability can be obtained. In this case, the blending amount is preferably in the range of 5 to 15% by weight.
[0081]
Whether it is polyfluoroethylene, polyvinylidene fluoride or polyvinyl alcohol, if the blending amount thereof falls below the lower limit value of each of the above ranges, the film formation may be adversely affected.
[0082]
In order to obtain a thin film of an ion conducting portion in which each fullerene derivative of this embodiment is bound by a binder, a known film forming method may be used including pressure molding and extrusion molding.
[0083]
【Example】
Hereinafter, the present invention will be specifically described based on examples.
[0084]
Example 1
Using the apparatus shown in FIG. 1, a sputtering target, a vibrator, and a container were installed, and conductive powder and a ball were placed in the container. The sputter target was platinum having a particle size of 100 mm. The ball is a stainless steel ball having a diameter of 3 mm, and the conductive powder has a surface area of 800 m.²/ G, carbon powder having an oil absorption of 360 ml / 100 g was used. Then, sputtering was performed using the vibrator while generating vibration with an amplitude of ± 5 mm and a vibration frequency of 36 Hz.
[0085]
Under the conditions described above, 1 g of carbon powder and 35 g of stainless steel balls are placed in the container, Ar (1 Pa) is introduced as the gas, 400 W RF is applied to the target, and the carbon powder and balls are applied. On the other hand, when sputtering was performed for 30 minutes while applying vibration with a vibrator, the weight of the carbon powder increased to 1.66 g, and 0.66 g of platinum adhered to the carbon. This corresponds to the weight ratio of 40 wt% Pt-supported carbon.
[0086]
Next, a solvent formed by kneading a binder made of Teflon (registered trademark) and carbon (without platinum) on the carbon sheet was applied to a thickness of 20 μm after drying. did.
[0087]
Further, the platinum-supported carbon powder obtained by the above method is kneaded with perfluorosulfonic acid as a binder and nPA (normal propyl alcohol) as an organic solvent, and this mixed solution is placed on a carbon sheet. It was applied and dried on the soaking prevention layer. The coating thickness after drying was 10 μm. This is referred to as the gas diffusible catalyst electrode of Example 1. This gas diffusive catalyst electrode was disposed on both sides of an ion exchange membrane (perfluorosulfonic acid) to produce a fuel cell as shown in FIG. 7, and the output was measured. The output obtained in Example 1 (unit: mW / cm²) As a relative value, which was 100%.
[0088]
Example 2
  Using the apparatus shown in FIG. 4, a sputter target, a vibrator, and a container are installed, and a part integrally formed so that the wire forms a spiral pattern when seen in a plan view is placed on the bottom surface of the container. It installed in the fixed state and arrange | positioned the said electroconductive powder on this component. This part was formed from a stainless steel wire having a diameter of 1.6 mm, and its outer diameter was 5 mm smaller than the inner diameter of the container, and the pattern pitch was 5 to 10 mm. As described above, since this component is placed on the bottom surface of the container in an unfixed state as described above, when platinum is deposited on the surface of the carbon powder by sputtering, it vibrates with the carbon powder.
[0089]
A fuel cell as shown in FIG. 7 was produced in the same manner as in Example 1 except that platinum was attached to the surface of the carbon powder using this apparatus. When the output of this fuel cell was measured, an output of 120% was obtained with respect to Example 1.
[0090]
Example 3
A fuel cell as shown in FIG. 7 was produced in the same manner as in Example 1 except that the oil absorption of the carbon powder supporting platinum was 150 ml / 100 g. When the output of this fuel cell was measured, an output of 65% with respect to Example 1 was obtained.
[0091]
Example 4
The specific surface area of carbon powder supporting platinum is 200m.²A fuel cell as shown in FIG. 7 was produced in the same manner as in Example 1 except that the amount was / g. When the output of this fuel cell was measured, an output of 65% with respect to Example 1 was obtained.
[0092]
Comparative Example 1
A liquid phase method was used for supporting platinum on the carbon powder. Carbon powder is converted to hexaamine platinum (IV) chloride ([Pt (IV) (NH_Three)₆] Cl_Four) Ion exchange was performed by dipping in an aqueous solution at room temperature for 1 hour. Next, this was washed and then reduced at 180 ° C. in a hydrogen stream to obtain a platinum-supported powder. A fuel cell as shown in FIG. 7 was produced and the output was measured in the same manner as in Example 1 except that this platinum-supported powder was used as the conductive catalyst particles. An output of 50% was obtained.
[0093]
Comparative Example 2
As shown in FIG. 7, in the same manner as in Example 1 except that platinum was adhered to the surface of the carbon powder by sputtering without using the ball as the vibration amplifying means and without vibrating. A fuel cell was fabricated. When the output of this fuel cell was measured, an output of 30% was obtained with respect to Example 1.
[0094]
Comparative Example 3
Except for placing the carbon powder as the conductive powder without placing the ball in the container of the vibration device, and adhering the platinum by sputtering while vibrating, the same as in Example 1. A fuel cell as shown in FIG. 7 was produced. When the output of this fuel cell was measured, an output of 60% was obtained with respect to Example 1.
[0095]
As is clear from the above, the manufacturing method according to the present invention is arranged such that the carbon powder as the conductive powder and the ball as the vibration amplifying means are arranged on the vibration surface, and these are vibrated, Since the catalytic substance such as platinum is attached to the surface of the carbon powder by the physical vapor deposition method such as sputtering, the carbon powder is more vibrated and does not stay at one place on the vibration surface. . Therefore, the platinum can be uniformly adhered to the entire carbon powder disposed in the container. And the fuel cell produced using the said gas-diffusible catalyst electrode containing this electroconductive catalyst particle obtained much higher output.
[0096]
Further, in the production method according to the present invention, platinum as the catalyst substance is attached to the surface of the carbon powder by the physical vapor deposition method such as sputtering. The conductive catalyst particles that can be attached only to the surface of the carbon powder can obtain good catalytic action in a smaller amount, and the contact area between the platinum and the gas is sufficiently secured. Therefore, the specific surface area of the platinum contributing to the reaction is increased, and the catalytic ability is also improved. And the fuel cell produced using the said gas-diffusible catalyst electrode containing this electroconductive catalyst particle obtained much higher output.
[0097]
In Example 3, since the oil absorption of the carbon powder supporting platinum was 150 ml / 100 g and less than 200 ml / 100 g, the gas permeability was likely to be lowered, and the output was sometimes lowered.
[0098]
In Example 4, the specific surface area of the carbon powder supporting platinum is 200 m.²/ G, 300m²Since it was less than / g, the characteristic as the said electroconductive catalyst particle tends to fall, and the output may fall.
[0099]
In Comparative Example 1, since the liquid phase method was used to support platinum on the carbon powder, the platinum was present in a spherical shape on the surface of the carbon powder, was easily detached, and the catalytic efficiency was low.
[0100]
Since the comparative example 2 did not use the ball as the vibration amplifying means when the platinum was deposited on the surface of the carbon powder by the sputtering method, and it was not vibrated, the vibration device according to the present invention was used. Platinum adhered only to the carbon powder present on the outermost surface of the container. Therefore, platinum could not be uniformly adhered to all the carbon powders in the container, and the output was lowered.
[0101]
In Comparative Example 3, the carbon powder was vibrated when platinum was deposited on the surface of the carbon powder by sputtering, but the balls as the vibration amplifying means were not used. On the other hand, platinum could not be uniformly deposited, and the output decreased.
[0102]
The embodiments described above can be variously modified based on the technical idea of the present invention.
[0103]
For example, although the ball or the spiral part is used as the vibration amplification means, a concentric part as shown in FIG. 5 or a folded part as shown in FIG. 6 may be used. In either case, excellent results equivalent to those of Example 2 were obtained.
[0104]
Moreover, although the said carbon powder was used as said electroconductive powder, in addition to this, the said ITO and SnO₂Etc. can also be used.
[0105]
Furthermore, although the said fuel cell using the said gas diffusible catalyst electrode obtained by the manufacturing method based on this invention was demonstrated, the said gas diffusible catalyst electrode is the reverse reaction of the said fuel cell. Can also be applied.
[0106]
[Effects of the invention]
According to the present invention, the catalyst material is disposed on the surface of the conductive powder by the physical vapor deposition while the conductive powder and the vibration amplifying unit are disposed on the vibration surface and are vibrated. Therefore, the conductive powder is more vibrated and sufficiently mixed, and does not stay at one place on the vibration surface. Accordingly, not only the surface of the powder layer but also the inside of the conductive powder comes to the surface, and the catalyst substance can be uniformly attached to all the conductive powder.
[0107]
  In addition, since the catalyst substance is attached to the surface of the conductive powder by the physical vapor deposition method, a catalyst substance having good crystallinity can be attached only to the surface of the conductive powder at a low temperature. The obtained conductive catalyst particles can obtain good catalytic action in a smaller amount, and a sufficient contact area between the catalyst substance and the gas is ensured, so that the catalyst substance that contributes to the reaction can be obtained. The specific surface area is increased and the catalytic ability is improved.
  In addition, the ionic conductor is adhered to the surface of the conductive powder, and the catalytic material is further adhered to the surface of the ionic conductor by the physical vapor deposition method, so that the crystallinity of the catalytic material is good. It is not necessary to perform heat treatment to make the catalyst material, and the catalyst substance can be adhered without impairing the performance of the ion conductor.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an apparatus for producing conductive catalyst particles according to the present invention.
FIG. 2 is a partially enlarged schematic view of the container in the manufacturing apparatus.
FIG. 3 is a partially enlarged schematic cross-sectional view of the manufacturing apparatus.
FIG. 4 is a schematic sectional view of a vibration device used in the manufacturing apparatus.
FIG. 5 is a schematic cross-sectional view of another vibration device.
FIG. 6 is a schematic cross-sectional view of still another vibration device.
FIG. 7 is a schematic configuration diagram of a fuel cell using a gas diffusing catalyst electrode obtained by the method for producing conductive catalyst particles according to the present invention.
FIG. 8 is a schematic configuration diagram of a hydrogen production apparatus using a gas diffusible catalyst electrode obtained by the production method.
FIG. 9 is a structural diagram of polyhydroxylated fullerene that is an example of a fullerene derivative that can be used in an embodiment of the present invention.
FIG. 10 is a schematic view showing an example of a fullerene derivative.
FIG. 11 is a schematic cross-sectional view showing conductive catalyst particles obtained by supporting platinum on carbon powder by a conventional manufacturing method.
FIG. 12 is a schematic cross-sectional view of an apparatus for producing conductive catalyst particles according to the prior invention.
FIG. 13 is a schematic cross-sectional view showing conductive catalyst particles obtained by the production method according to the present invention.
[Explanation of symbols]
1 ... conductive powder, 2 ... target, 3 ... ball, 4 ... container,
5 ... vibrator (electromagnetic coil type, etc.), 6 ... spiral vibration amplification means,
7 ... Concentric vibration amplifying means, 8 ... Folded vibration amplifying means,
9, 9 '... catalyst layer, 10, 10' ... gas permeable current collector,
11, 11 '... ion conducting part, 12, 14 ... terminal, 13, 13' ... negative electrode,
15, 15 '... positive electrode, 16 ... H₂Channel, 17 ... O₂Flow path,
18 ... catalyst substance (platinum), 19 ... ion conductor, 20 ... vibrating surface, 21 ... vibrating device

Claims (50)

While the conductive powder is vibrated, when the catalyst material is attached to the surface of the conductive powder by physical vapor deposition, the conductive powder and the vibration amplifying means are disposed on the vibration surface. In the method for producing conductive catalyst particles that are vibrated simultaneously , an ion conductor is attached to the surface of the conductive powder, and the catalyst substance is further attached to the surface of the ion conductor by the physical vapor deposition method. A method for producing conductive catalyst particles, which is characterized .   The method for producing conductive catalyst particles according to claim 1, wherein a ball is used as the vibration amplifying means, the conductive powder and the ball are mixed and placed in the same container, and the vibration is applied.   The method for producing conductive catalyst particles according to claim 2, wherein the balls are ceramic or metal balls having a diameter of 1 to 10 mm.   As the vibration amplifying means, a part in which the wire is formed integrally so as to form a spiral, concentric or folded pattern in plan view is used, and at least a part of the part is not fixed on the bottom surface of the container. The method for producing conductive catalyst particles according to claim 1, wherein the conductive powder is placed on the component and the vibration is applied to the component.   The method for producing conductive catalyst particles according to claim 4, wherein the wire formed in a spiral, concentric or folded pattern is a metal wire having a diameter of 1 to 10 mm.   5. The conductive catalyst particle according to claim 4, wherein the outer diameter of the component formed in a spiral, concentric or folded pattern is 5 mm smaller than the inner diameter of the container, and the pattern pitch is 5 to 15 mm. Production method.   The method for producing conductive catalyst particles according to claim 1, wherein a thickness or a diameter of the vibration amplifying unit is 10 to 70% with respect to a layer thickness formed by the conductive powder.   The method for producing conductive catalyst particles according to claim 1, wherein an area ratio of the vibration amplifying unit to a distribution region of the conductive powder is 30 to 80%.   2. The method for producing conductive catalyst particles according to claim 1, wherein a frequency of the vibration applied to the conductive powder and the vibration amplification means by a vibrator is 5 to 200 Hz.   The method for producing conductive catalyst particles according to claim 1, wherein an amplitude of the vibration applied to the conductive powder and the vibration amplifying unit by a vibrator is ± (0.5 to 20) mm.   The method for producing conductive catalyst particles according to claim 1, wherein a sputtering method using the catalyst substance as a target is used as the physical vapor deposition method.   The method for producing conductive catalyst particles according to claim 1, wherein a pulsed laser deposition method is used as the physical vapor deposition method.   The method for producing conductive catalyst particles according to claim 1, wherein the catalyst substance is attached to the conductive powder at a ratio of 10 to 1000% by weight. The method for producing conductive catalyst particles according to claim 1, wherein a noble metal material made of Pt, Ir, or Rh is used as the catalyst substance. The method for producing conductive catalyst particles according to claim 1, wherein the electric resistance of the conductive powder is 10 ⁻³ Ω · m or less. _2. The conductive catalyst particle according to claim 1, wherein the conductive powder is at least one of carbon, ITO (indium tin oxide: conductive oxide in which indium oxide is doped with tin), and SnO ₂ . Production method. The method for producing conductive catalyst particles according to claim 16 , wherein, when the carbon is used as the conductive powder, the specific surface area of the carbon is set to 300 m ² / g or more. The method for producing conductive catalyst particles according to claim 16 , wherein when carbon is used as the conductive powder, the oil absorption amount of the carbon is 200 ml / 100 g or more. A process of obtaining conductive catalyst particles by arranging a conductive powder and vibration amplifying means on a vibration surface, and adhering a catalyst substance to the surface of the conductive powder by physical vapor deposition while vibrating them. And a method for producing a gas diffusible catalyst electrode containing the obtained conductive catalyst particles, in the method for producing a gas diffusible catalyst electrode , attaching an ionic conductor to the surface of the conductive powder, Furthermore, the catalyst substance is adhered to the surface of the ion conductor by the physical vapor deposition method . The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein a ball is used as the vibration amplifying means, the conductive powder and the ball are mixed and placed in the same container, and the vibration is applied. 21. The method for producing a gas diffusing catalyst electrode according to claim 20 , wherein the ball is a ceramic or metal ball having a diameter of 1 to 10 mm. As the vibration amplifying means, a part in which the wire is formed integrally so as to form a spiral, concentric or folded pattern in plan view is used, and at least a part of the part is not fixed on the bottom surface of the container. The method for producing a gas diffusible catalyst electrode according to claim 19 , wherein the conductive powder is placed on the component and the vibration is applied. The method for producing a gas diffusive catalytic electrode according to claim 22 , wherein the wire formed in a spiral, concentric or folded pattern is a metal wire having a diameter of 1 to 10 mm. 23. The gas diffusive catalyst electrode according to claim 22 , wherein the outer diameter of the part formed in a spiral, concentric or folded pattern is 5 mm smaller than the inner diameter of the container, and the pattern pitch is 5 to 15 mm. Manufacturing method. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein the thickness or diameter of the vibration amplifying means is 10 to 70% with respect to the layer thickness formed by the conductive powder. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein an area ratio of the vibration amplifying means to a distribution region of the conductive powder is 30 to 80%. 20. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein a frequency of the vibration applied to the conductive powder and the vibration amplification means by a vibrator is 5 to 200 Hz. 20. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein an amplitude of the vibration applied to the conductive powder and the vibration amplification means by a vibrator is set to ± (0.5 to 20) mm. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein a sputtering method using the catalyst substance as a target is used as the physical vapor deposition method. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein a pulsed laser deposition method is used as the physical vapor deposition method. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein the catalyst substance is adhered to the conductive powder at a ratio of 10 to 1000% by weight. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein a noble metal material made of Pt, Ir or Rh is used as the catalyst substance. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein an electric resistance of the conductive powder is 10 ^-3 Ω · m or less. The gas diffusive catalyst electrode according to claim 19 , wherein the conductive powder is at least one of carbon, ITO (indium tin oxide: conductive oxide obtained by doping tin into indium oxide), and SnO _2. Manufacturing method. The method for producing a gas diffusive catalyst electrode according to claim 34 , wherein, when the carbon is used as the conductive powder, the specific surface area of the carbon is set to 300 m ² / g or more. The method for producing a gas diffusive catalyst electrode according to claim 34 , wherein when the carbon is used as the conductive powder, the oil absorption amount of the carbon is 200 ml / 100 g or more. The method for producing a gas diffusive catalyst electrode according to claim 19 , wherein the conductive catalyst particles are bound by a resin. The method for producing a gas diffusible catalyst electrode according to claim 19 , wherein the conductive catalyst particles are attached on a current collector to form a gas diffusible catalyst electrode. In the conductive catalyst particle manufacturing apparatus , comprising: vibration means for vibrating the conductive powder; physical vapor deposition means for attaching a catalyst substance to the surface of the conductive powder; and the vibration amplification means . An apparatus for producing conductive catalyst particles, wherein an ion conductor is attached to a surface of the powder, and further, the catalyst substance is attached to the surface of the ion conductor by the physical vapor deposition method . 40. The apparatus for producing conductive catalyst particles according to claim 39 , wherein a ball is used as the vibration amplifying means, the conductive powder and the ball are mixed and placed in the same container, and the vibration is applied. 41. The apparatus for producing conductive catalyst particles according to claim 40 , wherein the balls are ceramic or metal balls having a diameter of 1 to 10 mm. As the vibration amplifying means, a part integrally formed so as to form a spiral, concentric or folded pattern when used in a plane is used, and at least a part of the part is not fixed on the bottom surface of the container. 40. The apparatus for producing conductive catalyst particles according to claim 39 , wherein the apparatus is installed in a state, the conductive powder is disposed on the component, and the vibration is applied. 43. The apparatus for producing conductive catalyst particles according to claim 42 , wherein the wire formed in a spiral, concentric or folded pattern is a metal wire having a diameter of 1 to 10 mm. 43. The conductive catalyst particle according to claim 42 , wherein the outer diameter of the part formed in a spiral, concentric or folded pattern is 5 mm smaller than the inner diameter of the container, and the pattern pitch is 5 to 15 mm. Manufacturing equipment. 40. The apparatus for producing conductive catalyst particles according to claim 39 , wherein a thickness or a diameter of the vibration amplifying means is 10 to 70% with respect to a layer thickness formed by the conductive powder. 40. The apparatus for producing conductive catalyst particles according to claim 39 , wherein an area ratio of the vibration amplification means to a distribution region of the conductive powder is 30 to 80%. 40. The apparatus for producing conductive catalyst particles according to claim 39 , wherein a frequency of the vibration applied to the conductive powder and the vibration amplification means by a vibrator is 5 to 200 Hz. 40. The apparatus for producing conductive catalyst particles according to claim 39 , wherein an amplitude of the vibration applied to the conductive powder and the vibration amplification means by a vibrator is ± (0.5 to 20) mm. 40. The apparatus for producing conductive catalyst particles according to claim 39 , wherein a sputtering method using the catalyst material as a target is used as the physical vapor deposition method. 40. The apparatus for producing conductive catalyst particles according to claim 39 , wherein a pulsed laser deposition method is used as the physical vapor deposition method.

Images